Process of treating fabric with sulfopropylated, organofunctional silanes and siloxanes



United States Patent PROCESS OF TREATING FABRIC WITH SULFO- PROPYLATED, ORGANGFUNCTIONAL SILANES AND SILOXANES Loren A. Haluska, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Original application Dec. 5, 1963, Ser. No. 328,164, now Patent No. 3,328,449, dated June 27, 1967. Divided and this application Dec. 5, 1966, Ser. No.

4 Claims. (Cl. 117-1395) where each R" is independently selected from hydrogen or aliphatic hydrocarbon radicals from 1 through 6 carbon atoms, Q is an alkylene radical of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, d is an integer of 0 or 1, R is an alkylene radical that separates Y and 80;, by three carbon atoms, M consists of hydrogen, the ammonium radical, or metal atoms, c is an integer of 1 through 3; b is an integer of 1 through 2, a is an integer of 1 through 2, and f is the reciprocal of the valence of M. Z consists of hydrogen atoms or monovalent hydrocarbon, alkoxy, beta-alkoxyalkoxy, phenoxy, acyloxy, or hydrocarbyl-substituted isocyanoxy radicals, and e is an integer of 2 or 3, the sum of e and a being 4.

The compositions of this invention can also consist of a siloxane with at least one unit of the formula where e is an integer of 0 through 2, and the other symbols are as defined above; any other units in the siloxane being of the formula where g is an integer with a value of 0 through 3, and A consists of hydrogen, monovalent hydrocarbon or halohydrocarbon radicals, alkoxy, beta-alkoxyalkoxy, acyloxy, ph-enoxy, hydrocarbyl-substituted isocyanoxy, or hydroxy radicals.

R can consist of any divalent hydrocarbon radical such as methylene, octadecylene, isobutylene, allylene, butadiylene, cyclohexylene, phenylene, tolylene, l-phenyl-ethylene; any divalent halohydrocarbon radical such as chlorobutylene, decafluorooctadecylene, 3-bromopropylene, 3-

chloroallylene, tetrafiuorophenylene; and any divalent hydrocarbon ether such as -CH CH OCH -ornomc :HocHi-, L

CH3 0 DH? s OCHT, -C o R can also be any trivalent hydrocarbon radical such as /CH2 CH OI-I -oH-c,r-t,,-,

CH2- I I CH=CHCH2 CH2CHCH2 any trivalent halohydrocarbon radicals such as or any trivalent hydrocarbon ether such as /CHz- CH0 C E 00112- -orno CH 8 m O CH2- R" can be hydrogen or any monovalent aliphatic hydrocarbon radical of 1 through 6 carbon atoms such as methyl, isopropyl, hexyl, cyclohexyl, etc.

Q can be any divalent alkylene radical of 2 through 4 carbon atoms, that separated the two N groups by at least 2 carbon atoms, such as ethylene, propylene, butylene, isopropylene, etc.

| --NOH2OHN NCHCH2N-,

I CH2 CH3 l etc.

R can be any alkylene radical that separates Y and S0 by three carbon atoms such as propylene, isobu-tylene, 2-ethylpropylene, 1,2,3-trimethylpropylene, 2,2-dimethylpropylene, and

C H OCH CH O 0011.30 onomoetc.; any acyloxy radical such as acetate, propionate, isopropionate, isobutyrate, decanoate, etc.; phcnoxy; any hydrocarbyl-substituted isocyanoxy such as etc.

A can be a hydrogen atom; any monovalent hydrocarbon or halohydrocarbon radical such as methyl, chloromethyl, octadecyl, decabromooctadecyl, 3,3,3-trifiuoropropyl, vinyl cyclohexyl, perchlorocyclohcxyl, phenyl, iodophenyl, tolyl, isobutyl, etc.; any alkoxy radical such as methoxy, iso-propoxy, decoxy, ethoxy, etc.; any betaalkoxyalkoxy radical such as CH OCH CH O-,

etc.; any acyloxy radical such as acetate, propionate, isopropionate, isobutyrate, decanoate, etc.; phenoxy; any hydrocarbyl-substituted isocyanoxy such as and hydroxy radicals.

Infrared studies indicate that when Y is an amino group, internal and polymeric salts can be formed between the amino and sulfonate groups.

The compositions of this invention can be made by reacting a propane sultone of the formula Q'z-CQ: 0 CQr-SO: with compounds of the formula Z Si[-R(YM or with siloxane-containing units of the formula ?e O 4-a-e Si[R(YM1l)b]t\ where h is the valence of Y divided by the valence of M, each Q is a hydrogen atom or an alkyl radical, and the other symbols are identified above.

It should be noted that h can be fractional, i.e., that there may be more than one Y group per M group. For example, if Y is COO (monovalent) and M is calcium (divalent), then it is one-half; in other words, there are two Y groups attached to each calcium atom. But, if Y is N-- (divalent) and M is H (monovalent), then It is 2. In that case, there are two M groups per Y group.

The generic reaction for making the compositions of this invention is oQ'lo (z, i O VSi[R(YM CQ 2 vsnawrasomaau, where V symbolizes the rest of the molecule, consisting of Z and/or siloxane groups; the product being the composition of this invention.

For example, if we wish to react 3-hydroxy-1-propane sulfonic acid sultone with H VSiCHgCHzC ONa we can see that a equals 1, b equals 1, h equals 1/1 or 1, and f equals 1/1. Therefore, abh/f equals 1, i.e., one mole of sultone reacts with one mole of silyl group.

However, if we use CH CHzSOg instead of the above silyl compound, then 0 equals 1, b equals 2, h equals /2, and f equals /2. abh/f, therefore, equals 2, meaning that two moles of sultone can react with one mole of silyl group.

I1 and f are included in the expression abh/f to account for the case where Y and M are of unequal valence. For example, if we replace the above silyl compound with then (1 equals 2, b equals 1, h equals 3/1, and 1 equals 1/1; abh/f, therefore, equals 6; i.e., up to six moles of sultone will react with each mole of the above silyl compound.

This reaction can be run anywhere in the range of about 20 to C. A common solvent such as methanol or benzene is added to the reaction mixture along with the reactants. Heating of the reaction mixture should be with caution, for some of the reactions are exothermic, e.g. reactions where the primary amine is involved.

If the product is not an insoluble salt, as many of the metal salts are, an alkaline catalyst will often push the equilibrium of the reaction toward the product end, enhancing the yield.

The reactants can all be prepared by well-known processes; many of them are sold commercially.

The sultones shown above can be prepared by reacting sodium bisulfite with a compound of the following formula:

where Q is defined above. The reaction is as follows:

NaO g OH CQ'1=GQ,'CQ2OH O C Q,H-C Q: H acidity NaO s 0 o Q'r-( J 'oo'2oH o H CQ2-SO2/ Numerous other methods for preparing sultones are known to the art. For example, German Patent 1,107,220

discloses the method of heating gamma or delta-halosulfonic acid salts of sodium or ammonium in a vacuum, to obtain a sultone plus the halide of sodium or ammonium. German Patent 902,615 discloses the method of making sultones from aliphatic ether monosulfonic acids. A number of other methods can also be found in the literature.

The following examples are illustrative only and are not to limit this invention, which is properly delineated in the claims.

EXAMPLE 1 In a flask was placed 115.8 g. of

E [(CH3)2sio]n.t0(sioH2oHoH2NH CH3 CH3 CH3 1 CH CH3 EXAMPLE 2 In a flask was placed 111.2 g. of

(CH O) Si (CH NHCH CH Nl-l and 230 ml. of benzene. This was refluxed for one hour at 85-86 C. to remove moisture. The reaction mixture was 3 cooled to 31 C., and 61.1 g. of 3-hydroxy-1propane sulfonic acid sultone was added. Within two minutes the reaction temperature had increased to 48 C.

The product was stripped to 144 C. at 18 mm. pressure to remove the solvent. A product of the following structure was obtained:

(CHsO)aSiCHaCI-IuCHzNHCHeCI-IzNHCHQCI-IQCHQSOaH EXAMPLE 3 In a flask was placed 13.6 g. of

CH3 osiomoHooH 5.5 g. of sodium methoxide, and 77.7 g. of methanol. An exothermic reaction resulted.

To this mixture was added 12.2 g. of 3-hydroxy-1- propane sulfonic acid sultone, and the reaction mixture was refluxed at 65.5 C. for two hours.

The methanol was evaporated from the solution, and the product isolated. 25.8 g. of

CH3 0 'os10Hzoudoomomcmsoma was obtained as an amorphous solid.

EXAMPLE 4 In a 500 ml. flask was placed 20.1 g. of

77.7 g. of methanol, and 5.5 g. of sodium methoxide. The mixture was warmed in a range of 26.5 to 32 C. while an exothermic reaction took place, completely reacting the sodium methoxide.

Then 12.4 g. of 3-hydroxy-1-propane sulfonic acid sultone was added, and the reaction mixture was refluxed at 665 C. for 2 hours.

A pink, solid product was obtained on removing the methanol.

5 The product was belived to be 0 CHzCHaCHzSOaNa C H9 -CHzCH2CH S i- O 10 L 1H3 EXAMPLE 5 In a 500ml. flask was placed 27.8 g. of

(CHgO Si (CH NHCH CH NH and 45.9 g. of 3-hydroxy-1-propane sulfonic acid sultone was added over a 30 second period. The temperature of the reaction mixture rose from 28 C. to 94 C. without outside heating. On cooling, a hydroscopic solid was isolated with a formula:

GHQ omomsom EXAMPLE 6 In a 500 ml. flask was placed 19.6 g. of

30 (CH O) SiCH CH SH 100 ml. of methanol, and 5.49 g. of sodium methoxide. The temperature of the reaction mixture rose slightly, indicating the formation of (CH O) SiCH CH- SNa.

12.2 g. of 3-hydroxy-1propane sulfonic acid sultone was added to the mixture at 31 C. The temperature rose to 44 C. The mixture was refluxed at 64.5 C. for three hours.

A white, solid precipitate was recovered on cooling that was believed to be EXAMPLE 7 When 300 g. of

Calls /s1o (OSIIfJH2CHCH2CI-I20Hlzho CsHaCls to CH2 R on is mixed with 90 g. of

5 (DH-CH2 o (DH-S02 CH3 in 500 g. of benzene, the following product is obtained:

0% CH3 /Si0) (osuomorromcmo CH2ICHCHSO3H]Z)1Q (35 fiHgCla 10 H2 CH3 EXAMPLE 8 When g. of

I it (01130 SiOa/2)5(OSiCHO onto-rump is mixed with 12.4 g. of

OH I ..O A:

are reacted with 5 g. of 3-hydroxy-l-propane sulfonic acid sultone, the following product is obtained:

0 CHzNGHzCHzCHzSOaH OSiOH2 H CHa CHaOCHzO aO 3 0/ H CHzFNCHzCHzCHzSOaH Oz Fa EXAMPLE 1!) When 50 g. of

I01 CBH13 CHaC-O /SiO (0 SiCHzOOHzCHCHzCHzSOsNHQm (CH3)2O=NO 50 SOaNH;

are reacted with g. of

CH2CH O CHPSO2 the following product is obtained:

EXAMPLE 11 When 10 g. of

| (EH2 CHzOCHa 3 r is reacted with 2.5 g. of 3-hydroxy-1-propane sulfonic acid sultone, the following product is obtained:

(cHasiom) /CH2SO3NHCH2CH2OH2SO3H O1 2SiCHzCFCF CFa CHzSO NHCH2CH2CHzSO3H 611, $1320 CH3 3 EXAMPLE 12 When 10 g. of

O (O i-CHa)z I a SiCHzOCHzSOzNH 4, N=O

CHs

is reacted with 3.1 g. of 3-hydroXy-1-propane sulfonic acid sultone, the following product is obtained:

(Di l-CH3):

I Cil a iiCHzQOHzSOzNCHaOHzCHaSOaH I CH3 N=C\ EXAMPLE 13 When 12 g. of

SiCHzCH=CHCH2CH2 ITTHCHzCHzCHzCHzNH:

NCHQCHNH CH I CH3 C2115 ON=C (CH O=NO 50 OMEHCHzOHzSOgNI-h and 6 g. of B-hydroxy-l-propane sulfonic acid sultone are reacted, the following product is obtained:

Cal-I CHzCHZCHzSOaH EXAMPLE 14 When g. of

wumsromomorromo=o O=OOGa is reacted with 9.6 g. of 3-hydroXy-1-propane sulfonic acid sultone, the following product is obtained:

were dissolved in 98 g. of CH OH. A 5 inch by 7 inch square of nylon fabric was dipped in this solution and dried in the air.

(B) 2 g. of

were dissolved in 98 g. of CH OH. A 5 inch by 7 inch square of nylon fabric was dipped in this solution and dried in the air.

(C) A 5 inch by 7 inch square of nylon fabric was not treated.

The three nylon squares were each rubbed in one direction several times with a glass rod. The squares were placed over but not in contact with cigarette ashes. Ashes were found to be picked up only by sample C.

EXAMPLE 16 When polyacrylic, polyolefin, and polyester fabrics are immersed in a solution of from 0.25 to 30 Weight percent of one or more of the compositions disclosed in Examples 1 through where M is hydrogen, and from 99.75 to 70 weight percent of a volatile solvent that does not react with the fabric or the solute to be used and the fabrics are dried, said fabrics have a reduced tendency to acquire a static electricity charge.

Suitable solvents for this use are, among others, water, methanol, ethanol, isopropanol, hexane, cyclohexane, octane, decane, benzene, toluene, acetone, diethylether, etc.

'In cases where siloxanes are employed, the mol percent of the snlfonate-containing siloxane units must be sufficiently high to impart an antistat effect to fabrics.

I claim:

1. The process of reducing the tendency of fabric to acquire a static electrical charge by (1) immersing said fabric in a solution of '(A) 0.25 to 30% by weight of a composition of the formula Z Si[R (Y[RS'o H] where R is selected from the group consisting of divalent and trivalent hydrocarbons, halohydrocarbon, and hydrocarbon ether radicals,

Y is selected from the group consisting of R" is independently selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals of 1 through 6 carbon atoms,

Q is an alkylene radical, of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, and

d is an integer of 0 through 1,

R is an alkylene radical that separates Y and S0 by three carbon atoms,

0 is an integer of 1 through 3,

b is an integer of 1 through 2,

a is an integer of 1 through 2,

Z is selected from the group consisting of hydrogen atoms and monovalent hydrocarbon, halohydrocarbon, alkoxy, beta-alkoxyalkoxy, phenoxy, acyloxy, and hydrocarbylsubstituted isocyanoxy radicals, and

e is an integer of 2 through 3, the sum of e+a being 4, and

(B) 99.75 to 70% by weight of a volatile solvent that is not reactive with the fabric or ingredient (A); and (2) drying the fabric. 2. The process of claim 1 where ingredient (A) is 3. The process of reducing the tendency of fabric to acquire a static electrical charge by (1) immersing said fabric in a solution of '(A) 0.25 to 30% by weight of a siloxane containing an effective amount of units of the formula l e 0 sam m'smHnm.

where R is selected from the group consisting of divalent and trivalent hydrocarbon, halohydrocarbon, and hydrocarbon ether radicals, Y is selected from the group consisting of R" is independently selected] from the group consisting of hydrogen and aliphatic hydrocarbon radicals of 1 through 6 carbon atoms,

Q is an alkylene radical, of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, and A is selected from the group consisting of hyd is an integer of through 1, drogen, mon-ovalent hydrocarbon and halo- R is an alkylene radical that separates Y carbon radicals, alkoxy, beta-alkoxyalkoxy,

and S0 by three carbon atoms, acyloxy, phenoxy, hydrocarby1,substituted c is an integer of 1 through 3, isocyanoxy, and hydroxy radicals; and b is an integer of 1 through 2, (2) drying the fabric. a is an integer of 1 through 2, 4. The process of claim 3 where ingredient (A) is Z is selected from the group consisting of hy- CH3 CH3 CH3 drogen atoms and monovalent hydrocar- I bon, halohydrocarbon, alkoxy, beta-alkoxyucnmsloll'fim"2T0HZCHCHQNCHZCHCHZSOSHh al koxy, phenoxy, acyloxy, and hydrocarbyl- CH:

t't ted l d subs 1 u lsocyanoxy radica s, an References Cited e is an integer of 0 through 2, any other units in the siloxane being of the formula UNITED STATES PATENTS A Sio 3,155,533 11/1964 Schaschl et a1 117-1395 3,164,481 1/1965 Shibe 1l7'139.5 2 3,197,333 7/1965 Schonfeldt et a1. 117139.5

Where WILLIAM D. MARTIN, Primary Examiner.

g is an integer with a value of 0 through 3,

and T. G. DAVIS, Assistant Examiner. 

1. THE PROCESS OF REDUCING THE TENDENCY OF FABRIC TO ACQUIRE A STATIC ELECTRICAL CHARGE BY (1) IMMERSING SAID FABRIC IN A SOLUTION OF (A) 0.25 TO 30% BY WEIGHT OF A COMPOSITION OF THE FORMULA ZESI(R(Y(R''SO3H)C)B)A, WHERE R IS SELECTED FROM THE GROUP CONSISTING OF DIVALENT AND TRIVALENT HYDROCARBONS, HALOHYDROCARBON, AND HYDROCARBON ETHER RADICALS, Y IS SELECTED FROM THE GROUP CONSISTING OF 